Compositions comprising quaternary ammonium germicides and nonionic surfactants



United States Patent 01 ice 3,539,520 Patented Nov. 10, 1970 3,539,520COMPGSITIONS COMPRISING QUATER- NARY AMMONIUM GERMICIDES AND NONIONICSURFACTANTS Abraham Cantor, Elkins Park, Pa., and Murray W. Winicov,Flushing, N.Y., assignors to West Laboratories, Inc., Long Island City,N.Y., a corporation of New York No Drawing. Filed July 12, 1967, Ser.No. 652,685 Int. Cl. (111d 3/48 U.S. Cl. 252106 11 Claims ABSTRACT OFTHE DISCLOSURE Compositions comprising quaternary ammonium germicidesand nonionic detergents wherein unique compatibility with respect toperformance of the quaternary ammonium germicides is achieved in thepresence of amounts of detergent which are at least twice the amount ofgermicide, by employing a nonionic detergent in which the major portionof the molecule is made up of block polymeric C to C alkylene oxides,with alkylene oxide blocks containing C to C alkylene oxides and -45ethylene oxide providing a significant hydrophobic function, andalkylene oxide blocks containing ethylene oxides and 045% of C to Calkylene oxide providing a significant hydrophilic function.

Preferred compositions are detergent sanitizers con taining quaternaryammonium germicides in combination with 5 to times as much detergent. Insuch compositions enhanced and extended germicidal action can beprovided by employing as the nonionic detergent component adetergent-iodine complex, or by adding a PVP- iodine complex.

BACKGROUND OF THE INVENTION With the commercial introduction ofquaternary ammonium germicides (germicidal quats) about 25 years ago,the desirability of combining germicidal quates with detergents in theformulating of disinfecting and sanitizing products was immediatelyapparent. The then available anionic detergents were tried and foundunsuitable in such combinations due to reaction with the quaternaryammonium compound. When nonionic detergents became commerciallyavailable, it was initially thought that detergent-sanitizercompositions could be prepared with quaternary ammonium germicides'andvarying amounts of nonionic detergent.

The recognition that germicidal quats are adversely affected by hardwater came only shortly after the introduction of these chemicals ofphenomenally high phenol coefficient. Early literature on the subject ofcombinations of quats and nonionics was marked by conflicting reportsfrom reputable laboratories in which similar ratios of nonionic to quatwere shown to be effective or ineffective for apparently similar uses.The situation was complicated by the tendency to measure disinfectingproperties under prolonged kill time or stasis conditions. Not only waswater hardness frequently not considered as a factor, but the addedeffect of nonionic interference in the presence of hard water was notrecognized. Some investigators, working with distilled water, found thatnonionic detergents could increase germicidal performance of quats undercertain conditions, especially where prolonged kill times were used.

More recently, quat manufacturers found that certain quats were moreresistant to hard water than others. During this time ofiicialgovernment agencies began to rec- OgniZe the need for fast killingdetergent-quat performance in the presence of hard Water. The officialperformance test for detergent-sanitizers (e.g. nonionic-quatformulations) is given in the AOAC Tenth Edition, 1965, paragraphs 51023to 5.032 inclusive. This test prescribes a 30 second performance endpoint under hard water test conditions.

Quat manufactures, who acutally participated in the development of thismethod through industry-regulatory agency cooperation, quickly put aceiling on the amount (ratio) of nonionic which could be used withquats. This ceiling, universally adopted by the trade for the past tenyears, places a limit of from 1.5 to 2.0 parts of nonionic to one partof quat in a detergent-sanitizer formulation. At the same time, aminimum of 200 p.p.m. quat was, and is now, generally accepted as beingthe least amount of quat which can be safely recommended in adetergentsanitizer use dilution based on a conventional nonionic andgermicidal (even hard water) quat. This means, in effect, that useconcentrations containing 200 p.p.m. quat limited to 400 p.p.m. ofdetergent are significantly below the generally recognized level ofabout 1000 p.p.m. (0.1%) of nonionic, which is necessary for light dutyhard surface detergency. For many diflicult cleaning jobs, ten timesthis amount of detergent is indicated. At-the present time, therefore,quat-nonionic detergent-sanitizers are not used for this purpose in partbecause of the prohibitive cost of the concomitant quat germicide. Forexample, at todays prices, germicidal quats cost from 5 to 10 times asmuch as the widely used nonionic detergents.

THE INVENTION The present invention resides in the discovery that theexpected interference of nonionic detergent with germicidal quats can beavoided, paving the way for the formulating of compositions containingboth germicidal quats and nonionic detergents without the traditionallimitation on the proportions of components, by selecting the detergentfrom a limited class of nonionic detergents in which the major portionof the molecule is made up of block polymeric C C' alkylene oxides, withalkylene oxide blocks containing C to C alkylene oxides and 0-45ethylene oxide providing a significant hydrophobic function, andalkylene oxide blocks containing ethylene oxide and 0-45 of C to Calkylene oxide providing a significant hydrophilic function. Suchdetergents, while preferably built up from an alkylene oxide chainstarting group, can have as a starting nucleus almost any activehydrogen containing group including, without limitation, amides,phenols, and secondary alcohols.

The reason for the unique compatibility of the type nonionic detergentsabove described with germicidal quats is not understood, but it appearsto be in some way tied to the block polymer nature of the detergents andparticularly to the presence of a C to C alkylene oxide block or a mixedethylene oxide and C to C alkylene oxide block providing a significantlyhydrophobic function in the detergent. Samples of various knowndetergents answering this description have consistently been found toperform satisfactorily in the new type compositions and to contrastsharply with more conventional nonionic detergents.

One group of detergents containing the characteristic block polymer ofpropylene oxide, and commercially available under the trademark Pluroniccan be represented by the formula:

Formula A )X( )y( )X where E and PO represent ethylene oxide andpropylene oxide respectively, equals at least 15, (EO equals 20 to 90%of the total weight of said compound, and the molecular weight is in therange of about 2000 to 15,000. Typical Pluronics which will hereinafterbe referred to are:

Another group of detergents appropriate for use in the new compositionscan be represented by the formula:

Formula B Alkoxy (EO,PO) (EO=,PO) H wherein the alkoxy group contains 1to 20 carbon atoms, the weight percent of E0 is within the range of O to45% in one of the blocks a, b, and within the range of 60 to 100% in theother of the blocks a, b, and the total number of moles of combined EOand PO is in the range of 6 to 125 moles, with 1 to 50 moles in the POrich block and to 100 moles in the E0 rich block.

Typical detergents falling within Formula B above which may be employedin the new compositions include the following, identified in terms ofthe stated values for the difierent variables in the formula:

Moles Moles Carbon percent E0 plus plus in in a in P0 P0 alkoxy b in nin u Other examples of detergents of the general type embraced byFormula B include: Tergitol XD, Tergitol XH, and Tergitol X60 which arebutoxy derivatives of propylene oxide, ethylene oxide block polymershaving molecular weights within the range of about 2000-5000.

Other suitable detergents generally related to the above formulae, butcontaining polymeric butoxy (BO) groups can be represented as follows:

Formula C RO(BO),,(EO) H wherein R is an alkyl group containing 1 to 20carbon atoms, n is about 15 and x is about 15; and

Formula D where (EO) and (P0) are ethoxy and propoxy respectively, theamount of (PO) is such as to provide a molecular weight prior toethoxylation of about 300 to 7500, and the amount of (130),, is such asto provide about 20% to of the total weight of said compound.

The examples hereinafter appearing are directed essentially tocomparisons between compositions in which conventional germicidal quatsare associated with various nonionic detergents embraced by Formulas Ato E, and with other common nonionic detergents which are in extensivecommercial use. Such conventional germicidal quats, some of which willbe referred to in the examples include the following, identified bytrade name and chemical composition. Those identified with the asteriskare generally recognized as hard water quats.

Cationic germicide: Composition Hyamine 2389 Methyl dodecylbenzyltrimethyl ammonium chloride, and methyl dodecyl xylylene bis (trimethyl)ammonium chloride.

Beloran Lauryl benzyl diethanolammonium chloride.

*Tetrosan 3, 4 D Alkyl dimethyl 3, 4 dichlorobenzyl ammonium chloride.

*BTC 471 A1ky1** dimethyl ethylbenzyl ammonium chloride C 50%, C 30%, C17%, C 3%.

*BTC 927 Alkyl** dimethyl dimethylbenzyl ammonium chloride C 50%, C 30%,C 17%, C 3%.

*BTC 1100 Alkyl** dimethyl l-naphthylmethyl ammonium chloridemonohydrate C 98%, C 2%.

Emcol E607 N(lauroyl colaminoformylmethyl) pyridinium chloride.

*Hyamine 3500 N-alkyl (C12, C14, C dimethyl benzyl ammonium chloride.

Cetab Cetyltrimethylammonium bromide.

CPC Cetylpyridinium chloride.

LPC Laurylpyridinium chloride.

Hyamine 1622 Diisobutyl phenoxy ethoxy ethyl dimethylbenzyl ammoniumchloride.

For comparison purposes the examples include data for compositionsemploying a number of common nonionic detergents which are outside thescope of the invention, having the trade designations and chemicalidentifications as follows:

Igepal CO-710 Nonyl phenol-ethylene oxide condensate with 10-11 moles ofethylene oxide.

Igepal CO-880 Nonyl phenol-ethylene oxide condensate with about 30 molesof ethylene oxide.

Igepal CO-990 Nonyl phenol-ethylene oxide condensate with about 100moles of ethylene oxide.

Igepal AR660 Polyoxyethylene* fatty alkyl ether 60-65% ethylene oxideCm-Cm (3V. C14) Octyl phenol-ethylene oxide condensate with about 10moles of ethylene oxide.

Triton X100 from coco fatty acids x+y=5.

Ethomid HT60 As above from hydrogenated tallow x+y=50. Ethomid HTlS Asabove In the examples germicidal activity is measured by one of thefollowing test procedures:

Procedure A.The test procedure described in Ofificial Methods ofAnalysis of the Association of Official Agricultural Chemists, TenthEdition (1965) pp. 87-89 and page 80.

Procedure B.The following procedure, which involves slight modificationof Procedure A:

The test solution is prepared by appropriate dilution of a sample inwater of specific hardness (page 88). A sterile 250 ml. erlenmeyer flaskcontaining 99 ml. of the test solution is placed in a 20 C. constanttemperature water bath, and the solution is brought to temperature. A24- hour culture of S. choleraesuis ATCC No. 10708 grown in AOAC broth(page 80) is used as the test culture. This culture meets the AOACrequirements for phenol resistance, i.e., it is killed by a 1:90dilution of phenol in minutes, but not in .5 minutes, and it resists a1:100 dilution of phenol for minutes.

One ml. of the test culture is added to 99 ml. of the test solution heldat C. At the end of specified time intervals sec., 1 min., 2 min.), 1ml. of the culture-solution mixture is removed and diluted in 9 ml.Letheen neutralizer blank (page 87). One ml. and 0.1 ml. amounts of thisneutralizer dilution are plated in duplicate in Tryptone Glucose ExtractAgar containing Letheen (page 87) as a neutralizer. The plates areincubated at 37 C. for 48 hours. At the end of this time, the resultantcolonies are counted. The average counts per ml. when multiplied by theabove dilution made prior to plating gives the number of survivingorganisms per ml. of germicidal test solution.

The actual number of organisms (the challenge) originally subjected tothe action of the test solution is determined at the same time asfollows: One ml. of the test culture is added to 99 ml. of phosphatebuflFer (pH 7.2) dilution water (page 87) held at 20 C. At the end of 30seconds, 1 ml. of the culture-buffer mixture is transferred serially to3 bottles containing 100 ml. each of phosphate buffer dilution water.The final dilution is plated in duplicute in 1 ml. and 0.1 ml. amountsin Tryptone Glucose Extract Agar, and the resultant colonies counted.The average counts per ml. when multiplied by the above dilution figuregive the number of organisms (the challenge) actually subjected to theaction of the test solution. A comparison of this challenge count withthe number surviving in the test solution is the basis for calculatingthe percent reduction achieved by the test solution.

EXAMPLE I In standard 500 p.p.m. hard water germicidal detergentsolutions were prepared containing '200 p.p.m. of Hyamine 3500 andamounts of different nonionic detergents. These were tested by ProcedureB above described using 1 ml. S. clmlerasuis broth in 100 ml. of testsolution (3,000,000 organisms per ml. of test solution) and plate countsdetermined at /2 min., 1 min., and 2 min. inter vals. The resultsobtained are as follows:

Rdatgd Plate count, minutes Detergent quat kg 1 2 o Plnronic PEssentially the same results are obtained when the amount of PluronicP65 is increased to 10/1 or even to 1. Note in this connection that asoptimum proportions for most practical detergent sanitizer compositions,the detergent/ quaternary ratio should be in the 5/1 to 10/1 range.

EXAMPLE II Following the same procedure as described in Example I using500 p.p.m. hard water, solutions containing 200 p.p.m. of Beloran (whichis not a hard water quat) and various detergents in the amountsindicated were prepared and tested with the following results:

Ratio Plate count, minutes det./ Detergent quat 1 2 one c 14, 000 1, 40010 Igepal CO7l0 2/1 1,000, 000 50, 000 500 Do 5 1 1, 000,000 1, 000, 0001, 000, 000 Pluronic L44 5/1 13, 000 1, 600 30 Pluronic P54. 5/1 12, 500300 10 Pluronic P65. 5/1 12, 800 1,100 10 Pluronic L62. 5/1 26, 400 1,400 20 Plnronie P85. 5/1 6, 000 400 10 Pluronie P 4/1 64, 000 7, 200Tergitol XD 4/1 7, 300 3 10 Tergitol XH 4/1 26, 000 70 20 Ethomid C/15.5/1 1, 000, 000 640, 000 320, 000 Ethomid HT60- 5/1 1, 000, 000 700, 00028, 000 5/1 1, 000, 000 780, 000 180, 000 5/1 360, 13, 700 5/1 1, 000,000 1, 000, 000 1, 000,000 5/1 1, 000, 000 1, 000, 000 1, 000, 000 3/1660, 000 150, 000 8, 400 3/1 1, 000, 000 1, 000, 000 25,000 5/1 1, 000,000 1, 000, 000 1, 000, 000

In the foregoing tabulation it should be pointed out that Igepal CO-990which shows what might be considered borderline performance at the 5/1detergent/ quaternary ratio should be disregarded because this materialcontains so much ethylene oxide that it is no longer useful as adetergent.

EXAMPLE III Following the same procedure as described in Example I, butpreparing solutions in 300 p.p.m. hard water, solutions containing 200p.p.m. of different cationic germicides and the indicated amounts ofdifferent nonionic de- 7 tergents were prepared and tested, giving theresults shown in the following tabulations:

Plate counts, minutes Composition tested 1 2 Hyamine 3500 alone 10 10 10Plus 2/1 Igepal (JO-710- 12, 300 170 50 Plus 5/1 Igepal (30-710 1, 000,000 468, 000 103,000 Plus 5/1 Pluronic P65 10 10 Beloran alone..." 1,550 25 10 Plus 2/1 Igepal C 84, 500 6, 000 240 Plus 5/1 Igepal (30-710-820,000 470, 000 145, 000 Plus 5/1 Igepal AR660 1, 000, 000 880,000 510,000 Plus 5/1 Pluronic P65... 570 10 10 Emcol E607 alo11e 62, 500 5, 2001, 700 Plus 2/1 Igcpal (JO-710- 410, 099 195, 000 65, 000 Plus 5/1Igepal OO710 1, 000, 000 1, 000, 000 1, 000, 000 Plus 5/1 Pluronic P6571,000 3, 500 710 Hyamine 2389 alone 270, 000 108, 000 27, 000 Plus 5/1Igepal OO710 1, 000, 000 1, 000, 000 900, 000 Plus 5/1 Pluronic P65 520,000 35, 000 95, 000

The foregoing tabulation is of special interest in showing a substantialvariation in activity of the germicide alone, from the very quick actingHyamine 3500 to the much slower acting (but widely used commercially) Hyamine 2389. The advantage of Pluronic P65 over lgepal CO710 at the 5/1detergent/quaternary level is quite apparent with each of thegermicides, in spite of the differing activities of the germicides perse.

EXAMPLE IV Detergent-germicide solutions were prepared in 500 p.p.m.hard water using as germicide 200 p.p.m. of Tetrosan 3,4 D and varyingamounts of different detergents as indicated. The resulting solutionswere tested for germicidal activity by Procedure A above described usingE. coli as the test organism. The comparative results, at 30 sec. and 1min., expressed in plate count and percent, reduction in the number oforganisms, for the germicide alone and the germicide plus detergentunder the varied conditions are as follows:

8 ing organisms were equivalent to the quat alone; that is, there was nointerference with quat kill under these conditions.

EXAMPLE VI A number of solutions were prepared in water of differenthardness, as indicated, containing 200 p.p.m. of Hyamine 3500 anddetergents in the proportions indicated; and these solutions were testedaccording to Procedure A above using E. coli as the test organism withthe following results expressed in percent reduction in the number oforganisms:

Ratio Hard Result det./ Water, Detergent quat p.p.m. 30 sec. 1 min.

e 500 Igepal C07l0.- 2/1 500 Do 2/1 300 99. 8 Do 2/1 209 99. 991 D0 2/1100 99. 998 99. 999 D0- 2/1 DO 1/1 300 99.987 99. 999 D0- 1/1 100 99.993 99. 999 D 1 2 300 Amine oxide A 2/1 200 Amine oxide B 2/1 200 D0 2/1100 99. 724 99. 844 D0 2/1 50 99.758 99.996 D0 1/1 100 99.998 99. 999 Do 1/2 100 1 Passes. 2 Too numerous to count.

These results indicate clearly the effect of both water hardness anddetergent/quat ratio on the germicidal activity in the presence of theseconventional detergents. The results here are given for both the 30second and 1 minute kill merely to enable better visualizing of theseelfects. It should be noted, however, that to pass the test Procedure Athere must be at least a 99.999% reduction in the number of organisms in30 seconds; and

30 seconds 1 minute Ratio det./ Percent Percent D etergent quat Countreduction Count reduction EXAMPLE V A number of solutions were preparedin water of different hardness as indicated, containing Hyamine 3500alone at the 200 p.p.m. level, and Hyamine 3500 plus 2/1, 5/1 and 10/1ratios of difierent type detergents. These were tested by Procedure Babove described for 1 minute kill, and the plate counts of survivingorganisms are tabulated below.

in the following examples passing and failing results have referenceonly to the'3O sec. test.

EXAMPLE VII A number of solutions were prepared in 200 p.p.m. hard watercontaining 200 p.p.m. of Hyamine 3500 and 400 p.p.m. (2/1 detergent/quatratio) of various conventional detergents and block polymer detergents,and

Plate count at water hardness indicated, one

Ratio minute kill det.

Detergent quat 500 p.p.m. 300 p.p.m. 100 p.p.m. 0 p.p.m

None 10 10 10 10 Igepal GO-710 2/1 3,000 170 10 10 Do 5/1 500, 000 470,000 44, 000 10 Do. 10/1 1, 000, 000 1, 000, 000 1, 000,000 10 Pluronie P2/1 10 10 10 10 Do 5/1 10 10 10 10 Do 10/1 10 10 10 10 these solutionswere tested according to test Procedure A. The solutions containing theconventional detergents Igepal CO710, Myrj 78, Ethomid HT 15, AmineOxide A and Amine Oxide B all failed to pass this test.

The solutions containing the block polymer detergents Pluronics P65,P85, P105, P108 and P123, Tergitol XH, and Tetronic 704 (a compisitionaccording to Formula E in which the molecular weight prior toethoxylation is 2500-3000, and the molecular weight of the ethyleneoxide is 16002000) all passed the test. Also passing the test weresolutions in which the block polymers are identified as follows:

Block polymer A.a compound of the formula HO(C H O) (C H O) (C H O) Hhaving a molecular weight of approximately 4000 with equal parts byweight of ethylene oxide and propylene oxide.

Block polymer B.a compound similar to the Pluronics of Formula A inwhich the hydrophobe y contains about 90% PO and E0 and has a molecularweight of about 2500 and the hydrophile x+x contains about 90% E0 and10% PO and has a molecular weight of about 1700.

Block polymer C.-a compound similar to Block polymer B in which bothhydrophobe and hydrophile have molecular weights of about 2500.

EXAMPLE VIII A number of solutions were prepared in water of differenthardness, as indicated, containing 200 p.p.m. of Tetrosan 3, 4 D anddifierent detergents of the conventional type and the block polymer typein the proportions indicated. These solutions were tested according toProcedure A above using E. coli as the test organism with the followingresults:

EXAMPLE IX The procedure of Example VIII was repeated using a differentquaternary ammonium compound, BTC 471, at the 200 p.p.m. level, and anumber of conventional type detergents and block polymer detergents inthe amounts indicated. Testing of the solutions according to Procedure Agave the following results:

Ratio Hard det./ water, quat p.p.m. Result Conventional deter ents:

f. 800 Passes. Igepal C0710, 400 p p m 2/1 300 Fails. Myrj 53, 400 p pm-. 2/1 300 Do. Bryj 78, 400 p.p.m-. 2/1 300 D0. Ethomid HI15, 00 2/1500 Do. Amine oxide A 2/1 300 D0. Amine oxide B 2/1 300 Do. TritonX-100, 400 p.p.m 2/1 300 Do. Block Polymer detergents:

Pluronic P65, 400 p.p.m 2/1 300 Passes.

Do 2/1 800 Do. Pluronie P65, 4,000 p.p.m.. /1 500 Do. Block, Polymer D,400 pp. 2/1 300 Do. Block Polymer E, 400 p.p.m. 2/1 300 Do.

In the foregoing tabulation Block Polymer D is a nonionic detergentidentified by Formula B(a) and Block Polymer E is identified by FormulaB(g).

EXAMPLE X The Procedure of Example VIII was repeated using as quaternaryammonium compounds:

A-BTC 927 at 200 p.p.m. B-BTC 1100 at 200 ppm.

and typical conventional type and block polymer type detergents in theamounts indicated. Testing of the solutions according to Procedure Agave the following results:

In the formulating of germicidal detergent sanitizer products usingquaternary ammonium germicides it is frequently desirable to includeadded components such as builders, pH regulating additives, and/ororganic sequestering agents. It has been found that such additives canbe used in formulating products containing block polymer type detergentsof the present invention. This is demonstrated in the following example:

EXAMPLE XI A solution containing 200 p.p.m. of Hyamine 3500 and 500p.p.m. of Pluronic P65 (2.5/1 ratio of detergent/ quat) in 200 p.p.m.hard Water readily passes the Official AOAC germicidal and DetergentSanitizer Test-Procedure A.

Similar solutions were prepared containing additive in the amountsindicated and these were tested according to Procedure A with thefollowing results:

Additive Concentration, Solution, Type p.p.m. pH Result 400 11 Passes.400 3 Do. 200 10.8 Do. 200 10.8 Do.

1 Ethylene diarnine tetraaeetic acid sodium salt. 2 Sodiumtripolyphosphate.

The results when using the block polymeric material Pluronic P65 in theforegoing examples are characteristic of block polymer detergentsgenerally as embraced by Formulas A to E above. While there may be somevariation in organism kill obtained when switching from one blockpolymer to another as indicated in Example II or when switching from onecationic material to another as indicated in Example III, the use ofblock polymer detergents permits extensive variation of the detergent/quat ratio and of the water hardness without the severe restriction inthe functioning of the germicide which is characteristic of ordinarynonionic detergents.

The foregoing examples have clearly demonstrated the unusual freedomfrom interference with the germicidal quat by the special blockpolymeric nonionic detergents herein described when the detergent: quatratio is equal to or greater than 2:1, and even as high as :1. There isspecial value in being able to provide a nonionic detergent: germicidalquat ratio in the range of about 5:1 to 10:1 since this permits acombination of optimum germicidal action and optimum hard surfacedetergency in a single composition. The term germicidal quat as hereused is understood to embrace any quaternary ammonium compoundrecognized as having germicidal activity of practical significance. As aclass such quaternary ammonium compounds are characterized as having atleast one long chain alkyl or aryl group of 8 to 22 carbon atoms joinedto the quaternary nitrogen. Furthermore, germicidal activity which is ofpractical significance requires that the quaternary ammonium compoundhave a phenol coeflicient of at least 50, and preferably at 11 least100, with respect to S. aureus and S. typhosa at 20 C.

The preceding examples have demonstrated the superiority of blockpolymer nonionic detergents in situations where hard water is a factor.The present invention, however, extends into areas where distilled wateris used as the testing medium. The most important ofiicial test methodfor testing disinfactants to determine the maximum dilution which iseffective for practical disinfection is called the Use-Dilution Method.This method is described on pages 8284 of AOAC 1965) previously cited.Distilled water is used as the test medium.

By the way of background, it should be pointed out that the minimumamount of the most active quaternary ammonium compound accepted aspassing this test is 400 p.p.m. When formulating end use products withdetergents, builders, pH regulating additives, and/or organicsequestering agents for purposes of better cleaning, the quat level mayactually have to be increased, so that as much as 500 p.p.m. of quat arenecessary.

It has now been found that in contrast to such adverse performance inthe presence of conventional detergent, germicidal quats become moreeffective when combined with the block polymer nonionic detergents ofthe present invention. This is clearly demonstrated in the followingexample:

EXAMPLE XII Amounts in parts per million, p.p.m.

Pluronic Hyam1ne Igepal 3500 P65 P123 C0710 STPP NazCOa EDTA Results 50400 50 Do. 50 400 50 Passes. 50 400 50 Do.

In utilizing the present invention to formulate commercial products inthe field of detergent-sanitizers, it is within the scope of the presentinvention not only to combine compatible acids and alkaline substancesas normally employed in such products, but also to employ othercompatible active components in such products.

By way of illustration, in the detergent sanitizer field it isfrequently desired to have a single product both long sustainedgermicidal action and rapid kill of organisms. Some of the germicideswhich are most desirable for the sustained germicidal action are tooslow acting for the desired rapid kill performance. This problem can bemet by supplying the nonionic detergent as a detergent-iodine complex.The rapid kill germicidal activity of nonionic detergent-iodinecomplexes is well recognized in the art and some of the nonionicsembraced by Formulas A to B have been employed in detergent iodineproducts as detergent-sanitizers and the like.

The block polymeric nature of the nonionic detergents embraced byFormulas A to E makes them inherently capable of complexing with iodine,and while not all of the detergents would be detergents of choice forstraight detergent-iodine compositions, it is considered that any of thedisclosed nonionic detergents supplied as an iodine complex wouldeffectively supplent the activity of the germicidal quat.

In such a dual purpose detergent sanitizer the amount of iodine presentis preferably about 1 to 2 times the amount of germicidal quat, with theoptimum amount in each instance being dependent upon the relativeactivity 12 of the germicidal quat and the physical stability of theinherently complex formulation.

The following example illustrates a typical detergentsanitizercomposition of the present invention containing both germicidal quat andiodine.

EXAMPLE XIII A detergent sanitizer is prepared by combining:

The HI-I is first mixed with the Pluronic. The other components are thenadded in the order listed and mixed until a uniform clear dark-browncolored solution is obtained, the entire mixing being effected at roomtemperature.

This composition is a multipurpose detergent-sanitizer currently beingreadied for commercial distribution.

At 1:50 dilution in waters of normally varying hardness it is anexcellent heavy duty cleaner-sanitizer.

At 1:200 dilution the composition provides a good general purposedetergent-sanitizer, which passes the Use Dilution Confirmation TestAOAC. (1965 pages 82-84.

In this composition the major germicidal activity is the rapid activitywhich is provided by the iodine. The germicidal quat, however, fills animportant role. It provides a continuing germicidal action on surfacescoated with the composition.

EXAMPLE XIV A detergent sanitizer is prepared containing:

Percent Component: by weight Pluronic P-123 10.0 HII (57% I 1.75Tetrosan 3,4 D (60% act.) 1.8 PVP (polyvinylpyrrolidone) 5.0 Water 81.45

The order of mixing is not critical. The HII can be first mixed with thePluronic and the other components added, or the HII can be mixed withthe PVP aqueous solution and the other components added. Eitherprocedure leads to a similar distribution of complexed iodine betweenthe Pluronic and the PVP.

This is a stable product which readily dilutes to practical usesolutions. At a 1:100 dilution it is an effective general purposedetergent sanitizer.

The various examples have shown block polymer nonionic detergents withas few as 2 or 3 and as many as 8 blocks per molecule. The number ofblocks appears to be immaterial, and detergents with intermediatenumbers of blocks or higher numbers, as well as a greater number ofalternating blocks are within the scope of the invention provided theseblocks provide the essential hydrophobic and hydrophilic functionspreviously described.

Various changes and modifications in the versatile compositions of blockpolymeric nonionic detergents and germicidal quats herein disclosed willoccur to those skilled in the art, and to the extent that such changesand modi fications are embraced by the appended claims, it is to beunderstood that they constitute part of the present invention.

We claim:

1. A germicidal detergent composition consisting essentially of agermicidal quaternary ammonium compound and a nonionic detergent inwhich the major portion of the molecule is made up of block polymeric Cto C alkylene oxides, with alkylene oxide blocks containing C to Calkylene oxides and -45 ethylene oxide providing a significanthydrophobic function, and alkylene oxide blocks consisting of ethyleneoxide and 0-45 of C to C alkylene oxide providing a significanthydrophilic function, the nonionic detergent being a member selectedfrom the group consisting of the following formulae:

wherein EO and PO represent ethylene oxide and proylene oxide,respectively, y equals at least 15, (E0) equals 20-90% of the totalweight of said compound and the molecular weight is within the range ofabout 2,000 to 15,000;

wherein the alkoxy group contains 1-20 carbon atoms, EO and PO representethylene oxide and propylene oxide, respectively, the weight percent ofE0 is within the range of 0 to 45% in one of the blocks a, b and withinthe range of 60 to 100% in the other of the blocks a, b, and the totalnumber of moles of combined EO and PO is in the range of 6 to 125 moles,with 1 to 50 moles in the PO rich block and to 100 moles in the E0 richblock;

having a molecular weight of approximately 4000 with equal parts byweight of ethylene oxide and propylene oxide; and,

wherein EO and P0 are ethylene oxide and propylene oxide, respectively,the group (PO,EO) contains 90% PO and has a molecular weight of about2500, and the groups (EO,PO) contain about 90% E0 and have a molecularweight of about 1700, the minimum ratio of nonionic detergent toquaternary ammonium compound in said composition being not less than2:1, and in which composition said germicidal quaternary ammoniumcompound has a phenol coeflicient of at least 50 with respect to S.aureus and S. typhosa at 20 C., and is further characterized by havingat least one 8-22 carbon atom containing substituent selected from thegroup consisting of alkyl and aryl radicals which substituent is joinedto the quaternary nitrogen.

2. A germicidal detergent composition as defined in claim 1 wherein thenonionic detergent: quaternary ammonium compound ratio is in the rangeof about 5:1 to 10:1.

3. A germicidal detergent composition as defined in claim 1 wherein thenonionic detergent is a compound of Formula A.

4. A germicidal detergent composition as defined in claim 1 wherein thenonionic detergent is a compound of Formula B.

5. A germicidal detergent composition as defined in claim 1 wherein thenonionic detergent is a compound of Formula C.

6. A germicidal detergent composition as defined in claim 1 wherein thenonionic detergent is a compound of Formula D.

7. A germicidal detergent composition as defined in claim 1 wherein thenonionic detergent is a compound of Formula E.

8. A germicidal detergent composition as defined in claim 1 wherein thenonionic detergent is a compound of Formula F.

9. A germicidal detergent composition as defined in claim 1 wherein thenonionic detergent is a compound of Formula G.

10. A germicidal detergent composition as defined in claim 1 wherein thenonionic detergent component is a nonionic detergent-iodine complex, theamount of iodine in said complex being about one to two times the amountof said quaternary ammonium compound such as to provide additionalgermicidal activity.

11. A germicidal detergent composition as defined in claim 1, employinga complex of PVP-I, the amount of iodine in said complex being about oneto two times the amount of said quaternary ammonium compound such as toprovide additional germicidal activity.

References Cited UNITED STATES PATENTS 2,677,700 5/1954 Jackson et al.252152 2,739,922 3/1956 Shelanski 252-106 3,028,301 3/1962 Winicov252-106 X 3,223,643 12/1965 Law 252-106 3,337,463 8/1967 Schrnolka 25289MAYER WEINBLATT, Primary Examiner P. E. WILLIS, Assistant Examiner US.Cl. X.R.

